EP2877344B1 - Multilayer structures containing biopolymers - Google Patents
Multilayer structures containing biopolymers Download PDFInfo
- Publication number
- EP2877344B1 EP2877344B1 EP13822438.1A EP13822438A EP2877344B1 EP 2877344 B1 EP2877344 B1 EP 2877344B1 EP 13822438 A EP13822438 A EP 13822438A EP 2877344 B1 EP2877344 B1 EP 2877344B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- multilayer structure
- polymer
- acrylic
- biopolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001222 biopolymer Polymers 0.000 title claims description 54
- 239000010410 layer Substances 0.000 claims description 191
- 229920006112 polar polymer Polymers 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 38
- 239000000956 alloy Substances 0.000 claims description 27
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 27
- 229920000058 polyacrylate Polymers 0.000 claims description 24
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 22
- 239000004626 polylactic acid Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 239000011159 matrix material Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- -1 plastarch Polymers 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 16
- 239000004609 Impact Modifier Substances 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 239000012792 core layer Substances 0.000 claims description 11
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims description 10
- 229920001169 thermoplastic Polymers 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 229920005669 high impact polystyrene Polymers 0.000 claims description 9
- 239000004797 high-impact polystyrene Substances 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004566 building material Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 229920000298 Cellophane Polymers 0.000 claims description 2
- 229920000623 Cellulose acetate phthalate Polymers 0.000 claims description 2
- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 2
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000954 Polyglycolide Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920001800 Shellac Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229920002494 Zein Polymers 0.000 claims description 2
- 108010055615 Zein Proteins 0.000 claims description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 230000001413 cellular effect Effects 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 2
- 229940081734 cellulose acetate phthalate Drugs 0.000 claims description 2
- 229920006218 cellulose propionate Polymers 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- 150000007523 nucleic acids Chemical class 0.000 claims description 2
- 102000039446 nucleic acids Human genes 0.000 claims description 2
- 108020004707 nucleic acids Proteins 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920002961 polybutylene succinate Polymers 0.000 claims description 2
- 239000004631 polybutylene succinate Substances 0.000 claims description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001184 polypeptide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 2
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims description 2
- 229940113147 shellac Drugs 0.000 claims description 2
- 239000004208 shellac Substances 0.000 claims description 2
- 235000013874 shellac Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 150000008163 sugars Chemical class 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000005019 zein Substances 0.000 claims description 2
- 229940093612 zein Drugs 0.000 claims description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims 2
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims 2
- 229920002223 polystyrene Polymers 0.000 claims 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 238000003475 lamination Methods 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007771 core particle Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000010420 shell particle Substances 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 229940065472 octyl acrylate Drugs 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- GOZDOXXUTWHSKU-UHFFFAOYSA-N pentadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C=C GOZDOXXUTWHSKU-UHFFFAOYSA-N 0.000 description 2
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004790 ingeo Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012797 inorganic spherical particle Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- YOTGRUGZMVCBLS-UHFFFAOYSA-N pentadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C(C)=C YOTGRUGZMVCBLS-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0242—Acrylic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249991—Synthetic resin or natural rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31924—Including polyene monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
Definitions
- the invention relates to a multi-layer structure having at least one inner layer containing an alloy of a biopolymer and an acrylic polymer, and at least one outer layer containing a polar polymer matrix.
- the combination of outer polar layer and an inner biopolymer/acrylic layer provides improved properties, such as improved adhesion, and improved mechanial properties.
- the multi-layer structure may be in the form of a sheet, a film, a tube or pipe, or a profile, and could be used by itself or as a cap-layer over a substrate.
- Certain structural plastics such as high impact polystyrene (HIPS), acrylonitrile/butadiene/styrene (ABS) resins, poly(vinyl chloride) (PVC) resins, thermoplastic olefins (TPO), and the like, exhibit attractive mechanical properties when extruded, molded, or formed into various articles of manufacture.
- Such articles include, for example, bathtubs, shower stalls, counters, appliance housings and liners, building materials, doors, windows, siding, decking, railings and shutters, lawn and garden articles, marine articles, swimming pool articles, automotive components, and storage articles.
- the capstock generally is much thinner than the structural plastic, typically being about 5 to about 25% of the total thickness of the composite comprising the capstock and structural plastic plies.
- the thickness of the capstock can be about 0.05 to about 2.5 mm
- the thickness of the structural plastic ply can be about 1.0 to about 10 mm, and preferably from greater than 2 mm to 8 mm in thickness.
- Polar capstock layers including styrenic-based polymers, polyesters, polycarbonate, and polyvinylidene fluoride have been used over thermoplastic polyurethane (TPU), with specific tie layers, in US 61/623, 767 .
- TPU thermoplastic polyurethane
- Biopolymers are finding use as environmentally-friendly alternatives for many common plastics in typical applications, such as in packaging materials and bottling.
- Biopolymers can be defined either as polymers manufactured from a renewable carbon source, or as polymers that are biodegradable or compostable, or both. Most biopolymers suffer from poor physical properties and poor weatherability. For example polylactic acid is very brittle, resulting in very low impact properties of finished articles.
- US 7,666,946 and US 2012/0142823 describe the modification of biopolymers with up to 15 percent of an acrylic modifier.
- US 7,666,946 and US 2012/0142823 describe that biopolymers can be modified to improve properties with up to 15 percent of an acrylic modifier.
- JP2008062591A describes a stretched polylactic acid film laminated with a thin ( ⁇ 50 micron), heat sealable (Tg ⁇ 70°C), heat sealed polymer layer.
- JP2009066915A describes a multilayer film or sheet formed by laminating a plant-derived resin layer and a rubber reinforcing styrene resin layer.
- the multilayer structure suffers from limited resistance to UV rays. due to the nature of the described layers.
- a multilayer structure containing a layer of polar thermoplastic over a layer of a biopolymer/acrylic alloy has excellent physical properties, such as UV resistance, scratch resistance, chemical resistance, as well as good adhesion between juxtaposed layers, excellent impact strength, and ease of manufacture.
- the adhesion of a cap layer to a substrate is improved by using a biopolymer/acrylic alloy as a middle layer.
- the inner biopolymer/acrylic layer also improves the impact resistance of the multilayer structure.
- the addition of the biopolymer/acrylic alloy layer to the multilayer structure helps in the compatibility of the structure when used as rework.
- the invention relates to a multilayer structure comprising:
- the invention further relates to objects formed from the multilayer structure and means for producing these objects.
- the invention relates to a multi-layer structure in which one or more inner layers contain a biopolymer/acrylic alloy, and the outer layer(s) is a thermoplastic or thermoset polar polymer.
- the multilayer structures of the invention include films, sheets, profiles and articles having two or more structural layers.
- the structures may be planar, curved, angled or of any shape - including pipes, tubes, and hollow structures.
- structural layers is meant a layer included in the structure to provide specific properties to the structure.
- structural layer is meant to exclude adhesive or tie layers, though these may be present in the structure in addition to the two or more structural layers.
- the term "layer” refers to each of the two or more different materials that are secured to one another by any appropriate means, such as by inherent tendency of the materials to adhere to one another, or by inducing the materials to adhere by a heating, radiation, chemical, or any appropriate process.
- the layers may be held together by one or more adhesives or tie layers.
- a "different” layer means any change in the composition of the layer compared to another layer. Two identical layers could exist in the multilayer structure, as in the case of a three layer structure having an inner core layer and covered on both sides with identical layers.
- the terms “inner” and “outer” layers refer to the placement of the layers of the multilayer structure in regards to their exposure to the environment in a final article.
- the outer layer(s) is the layer to be exposed to the environment on one or both sides of an inner layer.
- the inner layer as used herein is meant a layer that is not meant to be exposed to the environment in its final use in an article. In a two-layer sheet, for example, the inner layer side will ultimately either be enclosed, or be placed against another material before final use.
- the outer layer(s) have a polar polymer matrix, while at least one inner layer has a matrix containing a biopolymer/acrylic alloy.
- the outer polar polymer layer of the invention may be formed by any means, including but not limited to coating, and extrusion.
- Each outer layer has a thickness of at least 0.5 microns, preferably at least 1 micron, and more preferably from 5 microns to 5 mm.
- the thinner layers represent dried coatings.
- Layers that are extruded have a thickness of at least 25 microns, preferably at least 50 microns, and more preferably greater than 75 microns, and most preferably greater than 100 microns.
- the inner biopolymer/acrylic layer has a thickness of 25 microns, preferably at least 50 microns, and more preferably greater than 75 microns, and most preferably greater than 100 microns.
- a polar polymer layer is directly next to a biopolymer/acrylic alloy layer - with no tie layer or adhesive between.
- the multilayer structure of this invention contains at least one thermoplastic polar polymer layer as an outer layer(s).
- the polar polymer layer contains a polar polymer matrix, the matrix making up at least 30 weight percent of the layer, preferably more than 50 weight percent, and more preferably at least 60 percent by weight.
- the polar polymer may be used without any additives, thereby making up 100 percent of the outer layer.
- the polar polymer matrix is a matrix of 100 weight percent of one polar polymer.
- the polar polymer is acrylonitrile-styrene-acrylate copolymers (ASA).
- ASA acrylonitrile-styrene-acrylate copolymers
- the styrenic polymers of the invention can be manufactured by means known in the art, including emulsion polymerization, solution polymerization, and suspension polymerization. Styrenic copolymers of the invention have a styrene content of at least 10 percent by weight, preferably at least 25 percent by
- the polar polymer has a weight average molecular weight of between 50,000 and 500,000 g/mol, and preferably from 75,000 and 150,000 g/mol, as measured by gel permeation chromatography (GPC).
- the molecular weight distribution of the acrylic polymer may be monomodal, or multimodal with a polydispersity index greater than 1.5.
- the polar polymer has a Tg of greater than 70°C.
- At least one inner layer of the inventive multi-layer structure contains an alloy of one or more acrylic polymers with one or more biopolymers.
- the acrylic and biopolymer materials are compatible, semi-miscible, or miscible. They should be capable of being blended in a ratio such that a single intimate mixture is generated without loss of mechanical integrity at usage temperature.
- the biopolymer acrylic alloy makes up at least 30 percent by weight of the layer, preferably at more than 50 weight percent, more preferably at least 75 weight percent, and most preferably at least 90 weight percent of the inner biopolymer/acrylic layer.
- the alloy contains 2 to 95 weight percent, preferably 5 to 90 weight percent, and more preferably 20-80 weight percent of acrylic polymer(s), and 5 to 98 weight percent, preferably 10 to 95 weight percent and more preferably 20 to 80 weight percent biopolymer(s).
- Biopolymer as used herein is meant to include polymers manufactured from a renewable carbon source, polymers that are biodegradable or compostable, or both.
- Biopolymers of this invention include, but are not limited to, polyesters, cellulosic esters, polyamides, starch and starch derivatives, shellac, sugars, polypeptides, nucleic acids, zein, cellophane, plastarch, polycaprolactone, polyglycolide, and chitosan.
- Useful polyesters include, but are not limited to, polylactic acid, polyhydroxyalkanoates, polycaprolactone, polyesteramide, polybutylene succinate, polyethylene adipate.
- a preferred polyester is polylactic acid.
- Useful cellulosic esters include, but are not limited to: cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate.
- the acrylic polymer in the alloy can be one or more of the previously listed acrylic polymers.
- the acrylic polymer in the alloy could be an acrylic impact modifier.
- the biopolymer/acrylic polymer alloy serves as the matrix polymer.
- the layer containing the biopolymer/acrylic is in a cellular or foamed form.
- the acrylic polymer, biopolymer, and optionally any additives can be blended in any order, and by any means known in the art to form the alloy.
- the components can be dry-blended prior to being melted, or directly melt blended together, such as in an extruder, or intimately mixed in a suitable solvent.
- the polar polymer matrix layer and biopolymer/acrylic polymer alloy may independently contain one or more additives.
- impact modifiers may be added into the polymer matrix.
- the impact modifier may be present at a level of from 0 to 80 weight percent, preferably 10 to 45, and more preferably from 20 to 40 weight percent, based on the total layer of matrix polymer and all additives.
- Impact modifiers useful in the invention include, but are not limited to, core-shell particles, block copolymers, and graft copolymers.
- Core-shell impact modifier is a multi-stage, sequentially-produced polymer having a core/shell particle structure of at least two layers.
- the core-shell modifier comprises three layers made of a hard core layer, one or more intermediate elastomeric layers, and a hard shell layer.
- the presence of a hard core layer provides a desirable balance of good impact strength, high modulus, and excellent UV resistance, not achieved with a core/shell modifier that possesses a soft-core layer.
- Hard layers are typically a single composition polymer, but can also include the combination of a small amount of a low Tg seed on which the hard core layer is formed. For example, a small 5% rubber core seed that becomes dispersed into a hard core layer would be included in the invention as a hard core layer.
- Hard layer can be chosen from any thermoplastic meeting the Tg requirements.
- a hard layer is composed primarily of methacrylate ester units, acrylate ester units, styrenic units, or a mixture thereof.
- Methacrylate esters units include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate and 2-methoxyethyl methacrylate.
- Acrylate ester units include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cycloheyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate and 2-methoxyethyl acrylate.
- the acrylate ester units are chosen from methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate.
- Styrenics units include styrene, and derivatives thereof such as, but not limited to, alpha-methyl styrene, and para methyl styrene.
- the hard layer is all-acrylic.
- At least one core or intermediate layer is elastomeric "soft layer", having a Tg of less than 0°C, and preferably less than -20°C.
- Preferred elastomers include polymers and copolymers of alkyl acrylates, dienes, styrenics, and mixtures thereof.
- a soft layer is composed mainly of acrylate ester units.
- Acrylate ester units useful in forming the soft block include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cycloheyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate and 2-methoxyethyl acrylate.
- the acrylate ester units are chosen from methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate.
- Useful dienes include, but are not limited to isoprene and butadiene.
- Useful styrenics include, but are not limited to alpha-methyl styrene, and para methyl styrene.
- the outer shell layer can be made of one or more shell layers, having a Tg > 0°C, more preferably Tg > 20 °C.
- the shell layer may be the same or different composition other "hard layers".
- the multi-stage polymer is a three stage composition wherein the stages are present in ranges of 10 to 40 percent by weight, preferably 10 to 20 percent, of the first stage (a), 40 to 70 percent, preferably 50 to 60, of the second intermediate stage (b), and 10 to 50 percent, preferably 20 to 40, of the final stage (c), all percentages based on the total weight of the three-stage polymer particle.
- the core layer is a polymethylmethacrylate - ethylacrylate copolymer
- the middle layer is a crosslinked polybutylacrylate-styrene copolymer
- the outer shell is a polymethylmethacrylate-ethylacrylate copolymer
- the multi-stage polymer can be produced by any known technique for preparing multiple-stage, sequentially-produced polymers, for example, by emulsion polymerizing a subsequent stage mixture of monomers in the presence of a previously formed polymeric product.
- the term "sequentially emulsion polymerized” or “sequentially emulsion produced” refers to polymers which are prepared in aqueous dispersion or emulsion and in which successive monomer charges are polymerized onto or in the presence of a preformed latex prepared by the polymerization of a prior monomer charge and stage. In this type of polymerization, the succeeding stage is attached to and intimately associated with the preceding stage.
- the refractive index of the core/shell particle matches the total refractive index of the matrix.
- match is meant that the refractive index of the core/shell particle should be within 0.03 units of the matrix polymer blend, and preferably within 0.02 units.
- the polar polymer and biopolymer/acrylic polymer matrix layers of the multilayer structures of this invention may further contain other additives typically present in polymer formulations, including but not limited to, stabilizers, plasticizers, fillers, coloring agents, pigments, antioxidants, antistatic agents, surfactants, toner, refractive index matching additives, additives with specific light diffraction, light absorbing, or light reflection characteristics, and dispersing aids.
- additives typically present in polymer formulations, including but not limited to, stabilizers, plasticizers, fillers, coloring agents, pigments, antioxidants, antistatic agents, surfactants, toner, refractive index matching additives, additives with specific light diffraction, light absorbing, or light reflection characteristics, and dispersing aids.
- an additive is provided to help prevent degradation of the layer composition upon exposure to radiation, such as high levels of UV radiation or gamma radiation.
- Useful radiation stabilizers include, but are not limited to poly(ethylene glycol), poly(propylene glycol), butyl lactate, and carboxylic acids such as lactic acid, oxalic acid, acetic acid, or a mixture thereof.
- an additive is provided to achieve specific light manipulation of the layer with specific light diffraction or light reflection characteristics.
- Useful additives include, but are not limited to polymeric or inorganic spherical particles with a particle size between 0.5 microns and 1,000 microns.
- the additive's refractive index is different from that of the matrix polymer, in order to achieve a haze higher than 10%.
- Layers of the multilayer structure of the invention may optionally be bonded by one or more tie layers or layers of adhesive.
- no tie layer or adhesive is used between the layer(s) of polar polymer and biopolymer/acrylic alloy.
- a tie layer may optionally be used as needed to obtain satisfactory adhesion between the layers or between the multi-layer sheet and a substrate.
- the tie layer could be provided into the multilayer structure during a coextrusion process, could be extrusion laminated, or can be applied during a lamination, press molding, or injection molding process. Any tie layer has an adhesive affinity to the layers on either side, and can be of any known composition.
- the tie layer contains a blend of adhesive compounds in which each component of the blend has a compatible, miscible, or semi-miscible chemistry to one of the layers.
- the tie layer is a copolymer having two or more functionalities, where each functionality has an affinity to a different layer.
- the multilayer structures of this invention may be produced by any method available in the art, such as by coating, co-extrusion techniques, lamination techniques, thermoforming, or any combination thereof. In one embodiment, co-extrusion is preferred. For acrylic covered biopolymer/acrylic alloy, a coating is preferred.
- Co-extrusion is a process in which two or more molten polymeric compositions are simultaneously extruded through a feedblock die or, alternatively, through a multi-manifold die, to form a laminar structure with different functional properties in each layer.
- feedblock die to feed a multimanifold die in a single process, which provides great flexibility in the manufacture of the multilayer structures of the invention.
- Lamination is the process of bonding together two or more prefabricated sheet or film layers by the use of adhesives, or by a combination of heat and pressure.
- hot melt lamination or thermal lamination brings two or more molten polymer layers together outside the extrusion die, usually at a nip roll or at the top roll of a roll stack.
- Extrusion lamination involves first a formation of one layer by any known process, followed by extrusion of a tie layer and/or second layer onto the first layer.
- a structure having polar polymer and biopolymer layers or an alloy of acrylic polymer and biopolymer is placed into a mold, and a substrate polymer is injected behind it.
- Coatings are applied at viscosities of 0,1 to 5000 cps, and preferably from 1 - 500 cps.
- the coating in the invention can be applied by any means known in the art, including but not limited to inkjet, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or by a spray apparatus.
- the coating is applied at a dry film thickness of 0.5 microns to 100 microns with a preferred range of 5 to 30 micron. Multiple coating layers can be applied sequentially. The coating could be done in-line or off-line, including by extrusion coating.
- the multilayer structure can have any given geometry, including but not limited to, a flat sheet, a rod, or a profile.
- the multilayer structure of the invention can be used by itself to form useful objects by known means, or can be combined with additional layers of materials.
- the multilayer structure can be in a sheet form and thermoformed into an object, including but not limited to, automotive parts, recreational vehicles, bathtubs, shower stalls, counters, appliance housings and liners, building materials, doors, windows, siding, decking, railings and shutters, lawn and garden parts, and storage containers.
- the multilayer structure could also be directly coextruded into a profile, such as, but not limited to, deck board, hand rail siding, and window profiles.
- the multilayer structure is used as a cap material to provide an aesthetic covering having improved weathering and durability to a substrate.
- the polar polymer forms the outer layer, and the biopolymer/acrylic layer is next to the substrate.
- the multilayer structure can be attached to the substrate either inherently using heat or radiation, or by the use of an adhesive or tie layer.
- the substrate layer is at least twice as thick as the capstock, preferably at least five times as thick.
- the substrate layer can be between 50 microns and 10 cm, preferably from 0.2 mm to 10 cm.
- the substrate may be another polymer (thermoplastic, elastomeric, or thermoset) such as non-limiting examples polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile/butadiene/styrene (ABS), styrene/butadiene or styrene/isoprene (SBS/SIS), hydrogenated SBS/SIS, polyolefin derivatives such as polypropylene, polyethylene, thermoplastic polyolefin copolymers, polyvinyl chloride (PVC), biopolymers, pultruded polyester or polyurethane composites; or can be a non-polymer material including, but not limited to paper, metal, ceramics, glass, etc.
- PS polystyrene
- HIPS high impact polystyrene
- ABS acrylonitrile/butadiene/styrene
- SBS/SIS styrene/butadiene or sty
- a single or multilayer structure that includes the outer polar polymer is used as a capstock over a biopolymer/acrylic substrate - forming a multi-layer structure.
- multi-layer structures anticipated by the invention include those listed below (PLA being used generically to mean PLA itself or where PLA can be substituted with other biopolymers). Based on the disclosure herein, one of ordinary skill in the art can imagine other useful structures of the invention.
- Reference Example 1 Demonstrating the adhesive strength of a three-layer sheet made of an acrylic outer layer over an inner layer of biopolymer/acrylic alloy over an acrylonitrile-butadiene-styrene (ABS) substrate.
- ABS acrylonitrile-butadiene-styrene
- All multilayer sheets showed excellent adhesion between both the Solarkote® A layer and the PLA/PMMA-IM layers and between PLA/PMMA-IM layers and the ABS layer. The layers could not be manually separated.
- Example 2 Comparing impact strength of coextruded sheet made of biopolymer acrylic inner layer with a polar polymer outer layer to a coextruded sheet made of acrylic inner layer with a polar polymer outer layer.
- Multiaxial impact testing would be performed at various temperatures, using a Instron Dynatup 9250G tester.
- the total energy reported in the case of A&C (having a PLA/PMMA-IM inner layer) would be expected to be significantly increased, as compared to B&D (having a PMMA-IM inner layer).
- Optical property measurements can be performed using a BYK Gardner Haze-Gard plus. Samples would be exposed to weathering in Florida. At 6 month intervals, optical properties would be measured. The use of an acrylic or ASA outer (F&G) layer would be expected to prevent deterioration of optical properties and prevent physical degradation of the sample as compared to pure PLA-IM (E) without an added outer layer.
- F&G acrylic or ASA outer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Description
- The invention relates to a multi-layer structure having at least one inner layer containing an alloy of a biopolymer and an acrylic polymer, and at least one outer layer containing a polar polymer matrix. The combination of outer polar layer and an inner biopolymer/acrylic layer provides improved properties, such as improved adhesion, and improved mechanial properties.
- The multi-layer structure may be in the form of a sheet, a film, a tube or pipe, or a profile, and could be used by itself or as a cap-layer over a substrate.
- Certain structural plastics, such as high impact polystyrene (HIPS), acrylonitrile/butadiene/styrene (ABS) resins, poly(vinyl chloride) (PVC) resins, thermoplastic olefins (TPO), and the like, exhibit attractive mechanical properties when extruded, molded, or formed into various articles of manufacture. Such articles include, for example, bathtubs, shower stalls, counters, appliance housings and liners, building materials, doors, windows, siding, decking, railings and shutters, lawn and garden articles, marine articles, swimming pool articles, automotive components, and storage articles.
- Although these structural plastics offer attractive property characteristics, the properties of their exposed surfaces can be less than ideal. That is, the surfaces of the structural plastics are degraded by light, can be easily scratched, and/or they can be eroded by common solvents. Consequently, it has become a practice in the industry to apply another resinous material over one or both sides of the structural plastic to protect the underlying structural material and provide a surface that can withstand abuse associated with the use environment. Such surfacing materials are called "capstocks".
- The capstock generally is much thinner than the structural plastic, typically being about 5 to about 25% of the total thickness of the composite comprising the capstock and structural plastic plies. For example, the thickness of the capstock can be about 0.05 to about 2.5 mm, whereas the thickness of the structural plastic ply can be about 1.0 to about 10 mm, and preferably from greater than 2 mm to 8 mm in thickness.
- Polar capstock layers including styrenic-based polymers, polyesters, polycarbonate, and polyvinylidene fluoride have been used over thermoplastic polyurethane (TPU), with specific tie layers, in
US 61/623, 767 - Biopolymers are finding use as environmentally-friendly alternatives for many common plastics in typical applications, such as in packaging materials and bottling. Biopolymers can be defined either as polymers manufactured from a renewable carbon source, or as polymers that are biodegradable or compostable, or both. Most biopolymers suffer from poor physical properties and poor weatherability. For example polylactic acid is very brittle, resulting in very low impact properties of finished articles.
US 7,666,946 andUS 2012/0142823 describe the modification of biopolymers with up to 15 percent of an acrylic modifier.US 7,666,946 andUS 2012/0142823 describe that biopolymers can be modified to improve properties with up to 15 percent of an acrylic modifier. -
JP2008062591A -
JP2009066915A -
US Application 13/390,625 US 2007/0276090 , andUS 2009/0018237 describe a blend of PLA matrix, acrylic polymer and a core/shell impact modifier having either a hard core layer or a soft core layer. - It is desired to produce a multilayer structure having a polar thermoplastic or thermoset polymer outer layer over a biopolymer layer that overcomes the problems of the structures of the art.
- Surprisingly it has been found that a multilayer structure containing a layer of polar thermoplastic over a layer of a biopolymer/acrylic alloy has excellent physical properties, such as UV resistance, scratch resistance, chemical resistance, as well as good adhesion between juxtaposed layers, excellent impact strength, and ease of manufacture. In one embodiment the adhesion of a cap layer to a substrate is improved by using a biopolymer/acrylic alloy as a middle layer. The inner biopolymer/acrylic layer also improves the impact resistance of the multilayer structure.
- As a further benefit, the addition of the biopolymer/acrylic alloy layer to the multilayer structure helps in the compatibility of the structure when used as rework.
- The invention relates to a multilayer structure comprising:
- a) at least one outer polar polymer layer comprising a polar polymer matrix
- b) at least one inner layer comprising a biopolymer/acrylic polymer alloy, wherin said thermoplastic polar polymer consists of acrylonitrile-styrene-acrylate (ASA) copolymers.
- The invention further relates to objects formed from the multilayer structure and means for producing these objects.
- The invention relates to a multi-layer structure in which one or more inner layers contain a biopolymer/acrylic alloy, and the outer layer(s) is a thermoplastic or thermoset polar polymer.
- All percentages used herein are weight percentages, unless otherwise specified, and all molecular weight are weight average molecular weights, unless otherwise specified.
- The multilayer structures of the invention include films, sheets, profiles and articles having two or more structural layers. The structures may be planar, curved, angled or of any shape - including pipes, tubes, and hollow structures. By structural layers is meant a layer included in the structure to provide specific properties to the structure. Specifically, the term structural layer is meant to exclude adhesive or tie layers, though these may be present in the structure in addition to the two or more structural layers.
- As used herein, the term "layer" refers to each of the two or more different materials that are secured to one another by any appropriate means, such as by inherent tendency of the materials to adhere to one another, or by inducing the materials to adhere by a heating, radiation, chemical, or any appropriate process. The layers may be held together by one or more adhesives or tie layers. A "different" layer means any change in the composition of the layer compared to another layer. Two identical layers could exist in the multilayer structure, as in the case of a three layer structure having an inner core layer and covered on both sides with identical layers.
- The terms "inner" and "outer" layers refer to the placement of the layers of the multilayer structure in regards to their exposure to the environment in a final article. The outer layer(s) is the layer to be exposed to the environment on one or both sides of an inner layer. The inner layer as used herein is meant a layer that is not meant to be exposed to the environment in its final use in an article. In a two-layer sheet, for example, the inner layer side will ultimately either be enclosed, or be placed against another material before final use. In the present invention the outer layer(s) have a polar polymer matrix, while at least one inner layer has a matrix containing a biopolymer/acrylic alloy.
- The outer polar polymer layer of the invention may be formed by any means, including but not limited to coating, and extrusion. Each outer layer has a thickness of at least 0.5 microns, preferably at least 1 micron, and more preferably from 5 microns to 5 mm. The thinner layers represent dried coatings. Layers that are extruded have a thickness of at least 25 microns, preferably at least 50 microns, and more preferably greater than 75 microns, and most preferably greater than 100 microns. The inner biopolymer/acrylic layer has a thickness of 25 microns, preferably at least 50 microns, and more preferably greater than 75 microns, and most preferably greater than 100 microns. In a preferred embodiment, a polar polymer layer is directly next to a biopolymer/acrylic alloy layer - with no tie layer or adhesive between.
- The multilayer structure of this invention contains at least one thermoplastic polar polymer layer as an outer layer(s). The polar polymer layer contains a polar polymer matrix, the matrix making up at least 30 weight percent of the layer, preferably more than 50 weight percent, and more preferably at least 60 percent by weight. The polar polymer may be used without any additives, thereby making up 100 percent of the outer layer. The polar polymer matrix is a matrix of 100 weight percent of one polar polymer. The polar polymer is acrylonitrile-styrene-acrylate copolymers (ASA). The styrenic polymers of the invention can be manufactured by means known in the art, including emulsion polymerization, solution polymerization, and suspension polymerization. Styrenic copolymers of the invention have a styrene content of at least 10 percent by weight, preferably at least 25 percent by weight.
- In one embodiment, the polar polymer has a weight average molecular weight of between 50,000 and 500,000 g/mol, and preferably from 75,000 and 150,000 g/mol, as measured by gel permeation chromatography (GPC). The molecular weight distribution of the acrylic polymer may be monomodal, or multimodal with a polydispersity index greater than 1.5. In a preferred embodiment the polar polymer has a Tg of greater than 70°C.
- At least one inner layer of the inventive multi-layer structure contains an alloy of one or more acrylic polymers with one or more biopolymers. The acrylic and biopolymer materials are compatible, semi-miscible, or miscible. They should be capable of being blended in a ratio such that a single intimate mixture is generated without loss of mechanical integrity at usage temperature. The biopolymer acrylic alloy makes up at least 30 percent by weight of the layer, preferably at more than 50 weight percent, more preferably at least 75 weight percent, and most preferably at least 90 weight percent of the inner biopolymer/acrylic layer.
- The alloy contains 2 to 95 weight percent, preferably 5 to 90 weight percent, and more preferably 20-80 weight percent of acrylic polymer(s), and 5 to 98 weight percent, preferably 10 to 95 weight percent and more preferably 20 to 80 weight percent biopolymer(s).
- "Biopolymer", as used herein is meant to include polymers manufactured from a renewable carbon source, polymers that are biodegradable or compostable, or both. Biopolymers of this invention include, but are not limited to, polyesters, cellulosic esters, polyamides, starch and starch derivatives, shellac, sugars, polypeptides, nucleic acids, zein, cellophane, plastarch, polycaprolactone, polyglycolide, and chitosan.
- Useful polyesters include, but are not limited to, polylactic acid, polyhydroxyalkanoates, polycaprolactone, polyesteramide, polybutylene succinate, polyethylene adipate. A preferred polyester is polylactic acid.
- Useful cellulosic esters include, but are not limited to: cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate.
- The acrylic polymer in the alloy can be one or more of the previously listed acrylic polymers. In one embodiment, the acrylic polymer in the alloy could be an acrylic impact modifier. In another embodiment, the biopolymer/acrylic polymer alloy serves as the matrix polymer.
- In one embodiment, the layer containing the biopolymer/acrylic is in a cellular or foamed form.
- The acrylic polymer, biopolymer, and optionally any additives (including impact modifiers) can be blended in any order, and by any means known in the art to form the alloy. For example, the components can be dry-blended prior to being melted, or directly melt blended together, such as in an extruder, or intimately mixed in a suitable solvent.
- The polar polymer matrix layer and biopolymer/acrylic polymer alloy, may independently contain one or more additives. In one embodiment impact modifiers may be added into the polymer matrix. The impact modifier may be present at a level of from 0 to 80 weight percent, preferably 10 to 45, and more preferably from 20 to 40 weight percent, based on the total layer of matrix polymer and all additives. Impact modifiers useful in the invention include, but are not limited to, core-shell particles, block copolymers, and graft copolymers.
- Core-shell impact modifier, as used herein, is a multi-stage, sequentially-produced polymer having a core/shell particle structure of at least two layers. Preferentially, the core-shell modifier comprises three layers made of a hard core layer, one or more intermediate elastomeric layers, and a hard shell layer. The presence of a hard core layer provides a desirable balance of good impact strength, high modulus, and excellent UV resistance, not achieved with a core/shell modifier that possesses a soft-core layer.
- "Hard layers" (Tg > 0°C, preferably Tg > 20 °C) are typically a single composition polymer, but can also include the combination of a small amount of a low Tg seed on which the hard core layer is formed. For example, a small 5% rubber core seed that becomes dispersed into a hard core layer would be included in the invention as a hard core layer. Hard layer can be chosen from any thermoplastic meeting the Tg requirements. Preferably, a hard layer is composed primarily of methacrylate ester units, acrylate ester units, styrenic units, or a mixture thereof. Methacrylate esters units include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate and 2-methoxyethyl methacrylate. Acrylate ester units include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cycloheyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate and 2-methoxyethyl acrylate. Preferably the acrylate ester units are chosen from methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate. Styrenics units include styrene, and derivatives thereof such as, but not limited to, alpha-methyl styrene, and para methyl styrene. In one embodiment the hard layer is all-acrylic.
- At least one core or intermediate layer is elastomeric "soft layer", having a Tg of less than 0°C, and preferably less than -20°C. Preferred elastomers include polymers and copolymers of alkyl acrylates, dienes, styrenics, and mixtures thereof. Preferably a soft layer is composed mainly of acrylate ester units. Acrylate ester units useful in forming the soft block include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cycloheyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate and 2-methoxyethyl acrylate. Preferably the acrylate ester units are chosen from methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and octyl acrylate. Useful dienes include, but are not limited to isoprene and butadiene. Useful styrenics include, but are not limited to alpha-methyl styrene, and para methyl styrene.
- The outer shell layer can be made of one or more shell layers, having a Tg > 0°C, more preferably Tg > 20 °C. The shell layer may be the same or different composition other "hard layers".
- Preferably the multi-stage polymer is a three stage composition wherein the stages are present in ranges of 10 to 40 percent by weight, preferably 10 to 20 percent, of the first stage (a), 40 to 70 percent, preferably 50 to 60, of the second intermediate stage (b), and 10 to 50 percent, preferably 20 to 40, of the final stage (c), all percentages based on the total weight of the three-stage polymer particle.
- In one embodiment the core layer is a polymethylmethacrylate - ethylacrylate copolymer, the middle layer is a crosslinked polybutylacrylate-styrene copolymer, and the outer shell is a polymethylmethacrylate-ethylacrylate copolymer.
- The multi-stage polymer can be produced by any known technique for preparing multiple-stage, sequentially-produced polymers, for example, by emulsion polymerizing a subsequent stage mixture of monomers in the presence of a previously formed polymeric product. In this specification, the term "sequentially emulsion polymerized" or "sequentially emulsion produced" refers to polymers which are prepared in aqueous dispersion or emulsion and in which successive monomer charges are polymerized onto or in the presence of a preformed latex prepared by the polymerization of a prior monomer charge and stage. In this type of polymerization, the succeeding stage is attached to and intimately associated with the preceding stage.
- In one embodiment the refractive index of the core/shell particle matches the total refractive index of the matrix. By match is meant that the refractive index of the core/shell particle should be within 0.03 units of the matrix polymer blend, and preferably within 0.02 units.
- The polar polymer and biopolymer/acrylic polymer matrix layers of the multilayer structures of this invention may further contain other additives typically present in polymer formulations, including but not limited to, stabilizers, plasticizers, fillers, coloring agents, pigments, antioxidants, antistatic agents, surfactants, toner, refractive index matching additives, additives with specific light diffraction, light absorbing, or light reflection characteristics, and dispersing aids.
- In one embodiment, an additive is provided to help prevent degradation of the layer composition upon exposure to radiation, such as high levels of UV radiation or gamma radiation. Useful radiation stabilizers include, but are not limited to poly(ethylene glycol), poly(propylene glycol), butyl lactate, and carboxylic acids such as lactic acid, oxalic acid, acetic acid, or a mixture thereof.
- In another embodiment, an additive is provided to achieve specific light manipulation of the layer with specific light diffraction or light reflection characteristics. Useful additives include, but are not limited to polymeric or inorganic spherical particles with a particle size between 0.5 microns and 1,000 microns. In a preferred embodiment, the additive's refractive index is different from that of the matrix polymer, in order to achieve a haze higher than 10%.
- Layers of the multilayer structure of the invention may optionally be bonded by one or more tie layers or layers of adhesive. In a preferred embodiment, no tie layer or adhesive is used between the layer(s) of polar polymer and biopolymer/acrylic alloy. A tie layer may optionally be used as needed to obtain satisfactory adhesion between the layers or between the multi-layer sheet and a substrate. The tie layer could be provided into the multilayer structure during a coextrusion process, could be extrusion laminated, or can be applied during a lamination, press molding, or injection molding process. Any tie layer has an adhesive affinity to the layers on either side, and can be of any known composition. In one embodiment, the tie layer contains a blend of adhesive compounds in which each component of the blend has a compatible, miscible, or semi-miscible chemistry to one of the layers. In other embodiments, the tie layer is a copolymer having two or more functionalities, where each functionality has an affinity to a different layer.
- The multilayer structures of this invention may be produced by any method available in the art, such as by coating, co-extrusion techniques, lamination techniques, thermoforming, or any combination thereof. In one embodiment, co-extrusion is preferred. For acrylic covered biopolymer/acrylic alloy, a coating is preferred.
- Co-extrusion is a process in which two or more molten polymeric compositions are simultaneously extruded through a feedblock die or, alternatively, through a multi-manifold die, to form a laminar structure with different functional properties in each layer. Of particular interest is the use of a feedblock die to feed a multimanifold die in a single process, which provides great flexibility in the manufacture of the multilayer structures of the invention.
- Lamination is the process of bonding together two or more prefabricated sheet or film layers by the use of adhesives, or by a combination of heat and pressure. Alternatively, hot melt lamination or thermal lamination brings two or more molten polymer layers together outside the extrusion die, usually at a nip roll or at the top roll of a roll stack.
- Extrusion lamination involves first a formation of one layer by any known process, followed by extrusion of a tie layer and/or second layer onto the first layer. In an extrusion molding process, a structure having polar polymer and biopolymer layers (or an alloy of acrylic polymer and biopolymer) is placed into a mold, and a substrate polymer is injected behind it.
- Coatings are applied at viscosities of 0,1 to 5000 cps, and preferably from 1 - 500 cps. The coating in the invention can be applied by any means known in the art, including but not limited to inkjet, roll-coat, brush-coat, gravure print, flexographic print, thermal transfer coat or by a spray apparatus. The coating is applied at a dry film thickness of 0.5 microns to 100 microns with a preferred range of 5 to 30 micron. Multiple coating layers can be applied sequentially. The coating could be done in-line or off-line, including by extrusion coating.
- The multilayer structure can have any given geometry, including but not limited to, a flat sheet, a rod, or a profile.
- The multilayer structure of the invention can be used by itself to form useful objects by known means, or can be combined with additional layers of materials.
- The multilayer structure can be in a sheet form and thermoformed into an object, including but not limited to, automotive parts, recreational vehicles, bathtubs, shower stalls, counters, appliance housings and liners, building materials, doors, windows, siding, decking, railings and shutters, lawn and garden parts, and storage containers.
- The multilayer structure could also be directly coextruded into a profile, such as, but not limited to, deck board, hand rail siding, and window profiles.
- In one embodiment, the multilayer structure is used as a cap material to provide an aesthetic covering having improved weathering and durability to a substrate. In this case, the polar polymer forms the outer layer, and the biopolymer/acrylic layer is next to the substrate. The multilayer structure can be attached to the substrate either inherently using heat or radiation, or by the use of an adhesive or tie layer. The substrate layer is at least twice as thick as the capstock, preferably at least five times as thick. The substrate layer can be between 50 microns and 10 cm, preferably from 0.2 mm to 10 cm. The substrate may be another polymer (thermoplastic, elastomeric, or thermoset) such as non-limiting examples polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile/butadiene/styrene (ABS), styrene/butadiene or styrene/isoprene (SBS/SIS), hydrogenated SBS/SIS, polyolefin derivatives such as polypropylene, polyethylene, thermoplastic polyolefin copolymers, polyvinyl chloride (PVC), biopolymers, pultruded polyester or polyurethane composites; or can be a non-polymer material including, but not limited to paper, metal, ceramics, glass, etc.
- In one embodiment, a single or multilayer structure that includes the outer polar polymer is used as a capstock over a biopolymer/acrylic substrate - forming a multi-layer structure.
- It was found that an outer polar polymer layer over an inner biopolymer/acrylic layer over a substrate surprisingly provides improved impact resistance.
- Some non-limiting examples of multi-layer structures anticipated by the invention include those listed below (PLA being used generically to mean PLA itself or where PLA can be substituted with other biopolymers). Based on the disclosure herein, one of ordinary skill in the art can imagine other useful structures of the invention.
- 1. Polar polymer (coating or extruded layer) over a PLA/acrylic layer, further used as a cap stock over a substrate.
- 2. A 3-layer construction of polar polymer/ PLA-acrylic alloy/polar polymer.
- 3. Polar polymer as a cap or coating over a PLA-acrylic substrate.
- 4. Any of the above structures 1-3 in which one or more of the layers is impact-modified.
- 5. Any of the above structures having an adhesive or tie layer between one or more layers.
- 6. Any of the above structures in which the substrate layer contains from 5 to 95 weight percent, and preferably from 20 to 80 weight percent of rework. The rework being recycled material of the whole multi-layer structure.
- 7. An outer layer that is a blend of an acrylic polymer, PLA, and polyvinylidene fluoride.
- Several multilayer sheets were made by coextrusion of an outer layer of an impact modifed acrylic (Solarkote® A) over a polylactic acid/acrylic modified with an acrylic impact modifier (PLA/PMMA-IM) inner layer over an ABS substrate layer. The PLA/PMMA-IM layer contained 33% acrylic core-shell impact modifier and PLA content was varied from 30 to 50% . (PLA used was Natureworks INGEO® 2003D)
- All multilayer sheets showed excellent adhesion between both the Solarkote® A layer and the PLA/PMMA-IM layers and between PLA/PMMA-IM layers and the ABS layer. The layers could not be manually separated.
- The following 2-layer sheets would be formed by coextrusion:
- A.) A acrylonitrile-styrene acrylic (ASA) outer layer and a PLA/PMMA-IM inner layer
- B.) An ASA outer layer and an acrylic polymer modified with an acrylic impact modifier (PMMA-IM) inner layer
- C.) A High Impact Polystyrene (HIPS) outer layer and a PLA/PMMA-IM inner layer
- D.) A HIPS outer layer and a PMMA-IM inner layer
- Examples B.), C.) and D.) do not belong to the invention.
- Multiaxial impact testing would be performed at various temperatures, using a Instron Dynatup 9250G tester. The total energy reported in the case of A&C (having a PLA/PMMA-IM inner layer) would be expected to be significantly increased, as compared to B&D (having a PMMA-IM inner layer).
- The following 2-layer sheets would be formed by coextrusion:
- E.) Extrusion of an PLA-IM sheet can be performed.
- F.) Coextrusion of a PLA-IM inner layer with an acrylic outer layer can be performed.
- G.) Coextrusion of a PLA-IM inner layer with an ASA outer layer can performed.
- Examples E.) and F.) do not belong to the invention.
- Optical property measurements can be performed using a BYK Gardner Haze-Gard plus. Samples would be exposed to weathering in Florida. At 6 month intervals, optical properties would be measured. The use of an acrylic or ASA outer (F&G) layer would be expected to prevent deterioration of optical properties and prevent physical degradation of the sample as compared to pure PLA-IM (E) without an added outer layer.
Claims (20)
- A multilayer structure comprising:a) at least one outer polar polymer layer comprising a polar polymer matrix consisting of a thermoplastic polymer, andb) at least one inner layer comprising a biopolymer/acrylic polymer alloy, wherein said thermoplastic polar polymer consists of acrylonitrile-styrene-acrylate (ASA) copolymers.
- The multilayer structure of claim 1, wherein said biopolymer/acrylic alloy layer comprises 2 to 95 weight percent of one or more acrylic polymers and 5 to 98 weight percent of one or more biopolymers.
- The multilayer structure of claim 1, wherein said biopolymer comprises at least one polymer selected from the group consisting of polyesters, cellulosic esters, polyamides, starch and starch derivatives, shellac, sugars, polypeptides, nucleic acids, zein, cellophane, plastarch, polycaprolactone, polyglycolide, chitosan, polylactic acid, polyhydroxyalkanoates, polycaprolactone, polyesteramide, polybutylene succinate, adipate. cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, polyhydroxy butyrate, and cellulose acetate phthalate.
- The multilayer structure of claim 3, wherein said biopolymer comprises polylactic acid, and/or polyhydroxy butyrate.
- The multilayer structure of claim 1, wherein said biopolymer layer has a polymer matrix comprising 20 to 100 percent of said biopolymer.
- The multilayer structure of claim 2, wherein said alloy comprises 20 - 80 weight percent of one or more acrylic polymers and 20 to 80 weight percent of one or more biopolymers.
- The multilayer structure of claim 1, wherein said acrylic polymer comprises at least 50 weight percent of methylmethacrylate units.
- The multilayer structure of claim 1, wherein one or more layers further comprises 5 to 60 weight percent of one or more impact modifiers, based on the total weight of the matrix polymer and all additives.
- The multilayer structure of claim 8 wherein said impact modifier is a core-shell impact modifier having a hard core layer and one or more shells with a Tg of greater than 0° C, and one or more intermediate elastomeric layers with a Tg of less than 0°C.
- The multilayer structure of claim 1 wherein one or more layers further comprises additives selected from the group consisting of stabilizers, plasticizers, fillers, coloring agents, pigments, antioxidants, antistatic agents, surfactants, toner, refractive index matching additives, additives with specific light diffraction, light absorbing, or light reflection characteristics, and dispersing aids.
- The multilayer structure of claim 1, wherein said structure further comprises one or more adhesive or tie layers.
- The multilayer structure of claim 1, wherein said multilayer structure further comprises a substrate layer, with said polar polymer layer, being on the outer side of the structure exposed to the environment, and said biopolymer/acrylic layer being between the substrate layer and the polar polymer layer.
- The multilayer sheet structure of claim 12 wherein said substrate is selected from the group consisting of glass, metal, ceramic, paper, thermoplastic polymers, thermoset polymers, polystyrene, polystyrene derivatives, high impact polystyrene (HIPS), acrylonitrile/butadiene/styrene (ABS), styrene/butadiene or styrene/isoprene (SBS/SIS), hydrogenated SBS/SIS), polyolefin derivatives, polypropylene, polyethylene, thermoplastic polyolefin copolymers, polyvinyl chloride (PVC), biopolymers, pultruded polyester, and polyurethane composites.
- The multilayer structure of claim 1 wherein a layer comprising said biopolymer/acrylic polymer alloy is in a cellular or foamed form.
- The multilayer structure of claim 1 where the overall structure thickness is from greater than 0.25 mm to 10 cm.
- The multilayer structure of claim 1 comprising an object selected from the group consisting of automotive parts, recreational vehicles, bathtubs, shower stalls, counters, appliance housings and liners, building materials, doors, windows, siding, decking, railings and shutters, lawn and garden parts, storage containers, deck board, hand rail siding, and a window profile.
- The multilayer structure of claim 1, wherein said structure comprises at least three-layers comprising: two outer-most layers comprising said polar polymer polymer, and at least one inner layer comprising said biopolymer/acrylic alloy, wherein said outer-most polar polymer layers may be the same or different in composition.
- The multilayer structure of claim 12, wherein said substrate comprises from 5 to 95 percent by weight of rework.
- The multilayer structure of claim 1, wherein said polar polymer layer is a coating of from 0.5 micron to 100 microns comprising at least 50 percent by weight of methylmethacrylate units.
- The multilayer structure of claim 1, wherein said polar layer has a thickness of greater than 50 microns and comprises a non-acrylic polymer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261676364P | 2012-07-27 | 2012-07-27 | |
PCT/US2013/052167 WO2014018817A1 (en) | 2012-07-27 | 2013-07-26 | Multilayer structures containing biopolymers |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2877344A1 EP2877344A1 (en) | 2015-06-03 |
EP2877344A4 EP2877344A4 (en) | 2015-12-02 |
EP2877344B1 true EP2877344B1 (en) | 2019-07-03 |
Family
ID=49997843
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13822438.1A Active EP2877344B1 (en) | 2012-07-27 | 2013-07-26 | Multilayer structures containing biopolymers |
Country Status (3)
Country | Link |
---|---|
US (1) | US10518508B2 (en) |
EP (1) | EP2877344B1 (en) |
WO (1) | WO2014018817A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160075866A1 (en) | 2014-09-12 | 2016-03-17 | Teknor Apex Company | Compositions for capstock applications |
CN104672739B (en) * | 2015-03-17 | 2017-06-23 | 昆山恒光塑胶股份有限公司 | Modified PS compound materials band and its manufacturing process |
JP6971236B2 (en) | 2015-12-18 | 2021-11-24 | スリーエム イノベイティブ プロパティズ カンパニー | Metal-containing sorbents for nitrogen-containing compounds |
WO2017112386A1 (en) | 2015-12-22 | 2017-06-29 | 3M Innovative Properties Company | Packaged pre-adhesive composition including a polylactic acid-containing packaging material, adhesives, and articles |
WO2017112450A1 (en) | 2015-12-22 | 2017-06-29 | 3M Innovative Properties Company | Internally incorporated phenolic resins in water-based (meth)acrylate adhesive compositions, pre-adhesive reaction mixtures, methods, and articles |
EP3448680A1 (en) * | 2016-04-26 | 2019-03-06 | 3M Innovative Properties Company | Film constructions and articles |
US10807344B2 (en) | 2016-04-28 | 2020-10-20 | Natureworks Llc | Polymer foam insulation structure having a facing of a multi-layer sheet that contains a heat resistant polymer layer and a polylactide resin layer |
CN109562589A (en) * | 2016-08-19 | 2019-04-02 | 敬道薄膜美洲有限责任公司 | Coextrusion polyethylene skin on polypropylene core |
US11731405B2 (en) * | 2017-11-16 | 2023-08-22 | Argotec, LLC | Polyvinylidene fluoride-acrylate and thermoplastic polyurethane multilayer protective film |
CN110724303B (en) * | 2019-09-27 | 2022-04-08 | 扬州市华裕包装有限公司 | Multilayer composite film and preparation method thereof |
EP4073298A1 (en) | 2019-12-10 | 2022-10-19 | Ticona LLC | Cellulose ester composition containing bloom resistant or bio-based plasticizer |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1942001A1 (en) * | 2005-11-30 | 2008-07-09 | Toray Industries, Inc. | Polylactic acid resin multilayer sheet and molded body made of same |
WO2011155731A2 (en) * | 2010-06-07 | 2011-12-15 | ㈜엘지하우시스 | Pla flooring material having fabric surface |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3944631A (en) * | 1974-02-01 | 1976-03-16 | Stauffer Chemical Company | Acrylate-styrene-acrylonitrile composition and method of making the same |
DE4121652A1 (en) * | 1991-06-29 | 1993-01-07 | Roehm Gmbh | Impact MODIFIERS |
KR100258600B1 (en) | 1997-10-06 | 2000-06-15 | 성재갑 | Melamine sheet laminated floorboard |
JP2002210886A (en) | 2001-01-19 | 2002-07-31 | Toray Ind Inc | Softened biodegradable resin stretched film |
US7179863B2 (en) | 2002-10-03 | 2007-02-20 | Arkema France | Use of a film based PVDF, PMMA or a blend thereof for covering articles made of a thermoset |
DE10339442B4 (en) * | 2003-08-25 | 2006-07-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Thermochromic polymer film and process for its preparation |
US7002754B2 (en) * | 2003-11-14 | 2006-02-21 | Case Western Reserve University | Multilayer polymer gradient index (GRIN) lenses |
EP1721936B1 (en) | 2004-03-05 | 2012-05-02 | Mitsubishi Rayon Co., Ltd. | Thermoplastic resin composition and molded article comprising the same |
JP5305590B2 (en) | 2004-06-16 | 2013-10-02 | ユニチカ株式会社 | Polylactic acid-containing resin composition and molded product obtained therefrom |
US20080241242A1 (en) | 2004-10-05 | 2008-10-02 | Francesco Caruso | Porous Polyelectrolyte Materials |
JP2007125836A (en) * | 2005-11-07 | 2007-05-24 | Tsutsunaka Plast Ind Co Ltd | Polylactic acid resin laminated body |
US8022139B2 (en) * | 2005-11-25 | 2011-09-20 | Kuraray Co., Ltd. | Polylactic acid composition |
US7666946B2 (en) | 2006-01-27 | 2010-02-23 | Arkema Inc. | Blends of biopolymers with acrylic copolymers |
JP5607285B2 (en) | 2006-06-23 | 2014-10-15 | 日本精工株式会社 | Bearing device |
JP2008062591A (en) | 2006-09-09 | 2008-03-21 | Tohcello Co Ltd | Polylactic acid based multilayer film |
CN101541853A (en) | 2006-11-21 | 2009-09-23 | 阿科玛股份有限公司 | Translucent and opaque impact modifiers for polylactic acid |
US7977397B2 (en) * | 2006-12-14 | 2011-07-12 | Pactiv Corporation | Polymer blends of biodegradable or bio-based and synthetic polymers and foams thereof |
JP2009066915A (en) | 2007-09-13 | 2009-04-02 | Nippon A & L Kk | Multilayer film or sheet |
US9267033B2 (en) * | 2007-10-01 | 2016-02-23 | Arkema Inc. | Blends of biodegradable polymers and acrylic copolymers |
US8658716B2 (en) * | 2007-10-03 | 2014-02-25 | Arkema France | Multilayer polymeric article having a metallic variegated look |
JP5283390B2 (en) | 2008-01-22 | 2013-09-04 | ロンシール工業株式会社 | Polylactic acid-based sheet or film and method for producing the same |
JP5405862B2 (en) | 2008-03-31 | 2014-02-05 | ウィンテックポリマー株式会社 | Multilayer tube |
JP2010052308A (en) * | 2008-08-29 | 2010-03-11 | Toppan Cosmo Inc | Decorative sheet |
EP2501760A4 (en) | 2009-11-17 | 2013-04-17 | Arkema France | Impact resistant acrylic alloy |
CN102712769B (en) * | 2010-01-29 | 2014-12-03 | 东丽株式会社 | Polylactic acid-based resin sheet |
FI124269B (en) | 2010-03-12 | 2014-05-30 | Stora Enso Oyj | Heat-sealable biodegradable packaging material, its manufacturing method and its product packaging |
KR101210156B1 (en) | 2010-11-09 | 2012-12-07 | 도레이첨단소재 주식회사 | Biodegradable multi-layer sheet having an excellent heat and inpact resistance and preparing process thereof |
KR101212386B1 (en) | 2010-11-09 | 2012-12-13 | 도레이첨단소재 주식회사 | Biodegradable multi-layer sheet having an excellent scratch resistance and transparent property and preparing process thereof |
KR101304144B1 (en) | 2011-05-13 | 2013-09-05 | (주)엘지하우시스 | Biodegradable sheet |
US20140147644A1 (en) | 2011-08-17 | 2014-05-29 | Arkema France | Multilayer polymer structures |
-
2013
- 2013-07-26 US US14/416,849 patent/US10518508B2/en active Active
- 2013-07-26 WO PCT/US2013/052167 patent/WO2014018817A1/en active Application Filing
- 2013-07-26 EP EP13822438.1A patent/EP2877344B1/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1942001A1 (en) * | 2005-11-30 | 2008-07-09 | Toray Industries, Inc. | Polylactic acid resin multilayer sheet and molded body made of same |
WO2011155731A2 (en) * | 2010-06-07 | 2011-12-15 | ㈜엘지하우시스 | Pla flooring material having fabric surface |
EP2578394A2 (en) * | 2010-06-07 | 2013-04-10 | LG Hausys, Ltd. | Pla flooring material having fabric surface |
Also Published As
Publication number | Publication date |
---|---|
EP2877344A4 (en) | 2015-12-02 |
WO2014018817A1 (en) | 2014-01-30 |
US20150174868A1 (en) | 2015-06-25 |
US10518508B2 (en) | 2019-12-31 |
EP2877344A1 (en) | 2015-06-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2877344B1 (en) | Multilayer structures containing biopolymers | |
EP2877403B1 (en) | Multilayer structures containing biopolymers | |
TWI297712B (en) | Acrylic polymer capstock with improved adhesion to structural plastics | |
US5318737A (en) | Feedblock coextrusion of modified acrylic capstock | |
CA2356338C (en) | Methods for manufacturing films with a layer containing mixtures of fluoropolymers and polyacrylates | |
JPH10291282A (en) | Laminated sheet or film, and its molded body | |
CA2653637C (en) | Method for the production of a biodegradable plastic film, and film | |
JP6670472B2 (en) | Moistureproof film for building materials | |
JP2000094602A (en) | Plastic composite sheet for thermoformable furniture of multilayer, furniture member manufactured by using the plastic composite sheet for the furniture, and manufacture of the plastic compotsite sheet for the furniture | |
ZA200609419B (en) | Polymer mixture consisting of an impact-resistance modified poly(meth)acrylate and a fluoropolymer | |
JPH06278255A (en) | Laminate made of polyamide/polyolefin alloy as base and article obtained using it | |
JP2008012689A (en) | Vinylidene fluoride resin laminated film and its manufacturing method | |
CA1061973A (en) | Matt and scratch-resistant films and process for their manufacture | |
JPH04503637A (en) | Sheet materials useful in forming protective and decorative coatings | |
JP2008087303A (en) | Decorative sheet for insert molding | |
JP6967520B2 (en) | Laminated decorative film and its manufacturing method, as well as decorative molded body and its manufacturing method | |
JP2788756B2 (en) | Fluororesin-based colored film and method for producing the same | |
JPH1052893A (en) | Co-extruded multilayer laminated sheet made of plastic and method for manufacturing molding using it | |
JP4580066B2 (en) | Fluororesin laminate and molded body comprising the same | |
US20080199675A1 (en) | Laminate film | |
JP2009274454A (en) | Decoration sheet | |
JP4266554B2 (en) | Vinylidene fluoride resin laminated film | |
WO2017073077A1 (en) | Injection-molded complex and decorative sheet, and methods for producing same | |
JP2001071428A (en) | Car decorating laminated sheet and production thereof | |
JPH1058618A (en) | Plastic coextrusion multi-layer laminated sheet and manufacture of molded item employing this |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20150123 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
RA4 | Supplementary search report drawn up and despatched (corrected) |
Effective date: 20151104 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B32B 5/18 20060101ALN20151029BHEP Ipc: B32B 27/30 20060101ALI20151029BHEP Ipc: B32B 27/20 20060101AFI20151029BHEP Ipc: B32B 3/26 20060101ALI20151029BHEP Ipc: B32B 27/06 20060101ALI20151029BHEP Ipc: B32B 27/36 20060101ALI20151029BHEP Ipc: B32B 27/08 20060101ALI20151029BHEP Ipc: B32B 7/12 20060101ALI20151029BHEP |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20170210 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B32B 27/20 20060101AFI20181207BHEP Ipc: B32B 27/36 20060101ALI20181207BHEP Ipc: B32B 27/06 20060101ALI20181207BHEP Ipc: B32B 3/26 20060101ALI20181207BHEP Ipc: B32B 5/18 20060101ALN20181207BHEP Ipc: B32B 27/08 20060101ALI20181207BHEP Ipc: B32B 7/12 20060101ALI20181207BHEP Ipc: B32B 27/30 20060101ALI20181207BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B32B 27/20 20060101AFI20190108BHEP Ipc: B32B 27/30 20060101ALI20190108BHEP Ipc: B32B 27/06 20060101ALI20190108BHEP Ipc: B32B 27/08 20060101ALI20190108BHEP Ipc: B32B 5/18 20060101ALN20190108BHEP Ipc: B32B 27/36 20060101ALI20190108BHEP Ipc: B32B 3/26 20060101ALI20190108BHEP Ipc: B32B 7/12 20060101ALI20190108BHEP |
|
INTG | Intention to grant announced |
Effective date: 20190124 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B32B 5/18 20060101ALN20190116BHEP Ipc: B32B 3/26 20060101ALI20190116BHEP Ipc: B32B 7/12 20060101ALI20190116BHEP Ipc: B32B 27/30 20060101ALI20190116BHEP Ipc: B32B 27/06 20060101ALI20190116BHEP Ipc: B32B 27/36 20060101ALI20190116BHEP Ipc: B32B 27/20 20060101AFI20190116BHEP Ipc: B32B 27/08 20060101ALI20190116BHEP |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1150476 Country of ref document: AT Kind code of ref document: T Effective date: 20190715 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602013057473 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20190703 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1150476 Country of ref document: AT Kind code of ref document: T Effective date: 20190703 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191104 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191003 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191003 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191103 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191004 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20190731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190726 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190731 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190731 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190731 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200224 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602013057473 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG2D | Information on lapse in contracting state deleted |
Ref country code: IS |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190726 |
|
26N | No opposition filed |
Effective date: 20200603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20130726 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602013057473 Country of ref document: DE Owner name: TRINSEO EUROPE GMBH, CH Free format text: FORMER OWNER: ARKEMA FRANCE, COLOMBES, FR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20210923 AND 20210929 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190703 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230602 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20230727 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230725 Year of fee payment: 11 Ref country code: DE Payment date: 20230727 Year of fee payment: 11 |